ES2246838T3 - RETICULATED ACRYLIC MICROPARTICLES, PREPARATION PROCEDURE AND APPLICATIONS IN COATINGS AND MOLDING PRODUCTS. - Google Patents

Abstract

The invention relates to cross-linked acrylic microparticles, a method for the production thereof by polymerization in a dispersion in a non aqueous medium and to the uses thereof in covering or moulding compositions involving a favourable compromise between hardness, flexibility and adhesion. The micropparticles are obtained from a composition comprising: 50-99% mols of a constitutent (A) consisting of Cardura E 10 (meth)acrylate and optionally alkyl (meth)acrylate in C2-C8; a compound (B) consisting of at least one monomer or oligomer having at least 2 ethylenic unsaturations; a compound (C) consisting of at least one monomer or oligomer having in addition to one ethylenic unsaturation at least one second function (F1) with the possibility of at least partial chemical modification of the initial functions f1 into final functions f2.

Description

Crosslinked acrylic microparticles, preparation procedure and applications in the coatings and molding products

The present invention relates to crosslinked acrylic microparticles of a composition particular, to a preparation procedure by polymerization in dispersion, in a non-aqueous medium, in the absence of stabilizing polymer, and to applications in the compositions of coating or molding, as a reactive or non-reactive component, which allows, through its presence, technical benefits improved, in terms of compromise between hardness, flexibility, and adhesion, on various substrates, without negatively affecting the other essential technical performance of the coatings or of the molding products concerned, or the application of these.

These microparticles and the compositions that contain, can be used in various fields of application, such as: protective varnishes, paints, adhesives, inks, powder-shaped materials for molding, products molding, loaded or not, composite materials (composites), that need technical performance significantly improved, at the same time, in hardness, flexibility, and adhesion on various substrates

The use ownership commitment, for a material, either a coating, or a product of molding, either a composite or "composite" material, is always difficult to obtain and, in a particular way, in terms of regarding a good commitment hardness / flexibility / adhesion.

A known procedure in order to improve The hardness / flexibility / adhesion commitment is the one consisting of incorporate, in a hard matrix, a softer additive, or inverse Thus, for example, the strengthening of the fragile matrices of the type epoxy / amine, can be done by adding thermoplastics or elastomer particles of the type core / wrap, as described "Toughened Plastics", - Reinforced plastics -, Adv. Chem. Series. No. 252 (1996) Ed. CK. Riew et AJ Kinlock, Am. Chem. Soc. Washington D.C. The inconvenient major of this solution, it is a very important increase of the viscosity of the formulations, which causes molding problems or application as a coating.

In the case of coatings, in order to increase the hardness, it is common to incorporate, in the formulation, multifunctional crosslinking agents to increase density of film crosslinking. The addition of these agents, entails an increase in internal tensions and heterogeneity of the matrix (Macromol. Chem. Phys., 1998, 1043-1049) and, consequently, a decrease in the flexibility and adhesion of the coating. The utilization of microparticles in the coatings, is described, already, in Prog. Org. Coat., 15, 1988, 373, to improve mechanical properties of the lining. Meanwhile, the increase in tension to the breakage is done at the expense of the flexibility of the material. By On the other hand, no effect on adhesion is described.

In fact, adhesion is also a key property for coatings and, for compositions of molding reinforced by loads. A general description of Adhesion phenomenon, is the one given in Handbook of Adhesion, - Adhesion manual -, (D.E. Packham, Longman Scientific & Technical, 1992). Adhesion depends, on the one hand, on the interactions between the substrate and the coating molecules and, on the other hand, of the mechanical properties of the coating. Generally, in a homologous series in chemical composition, a harder coating, will lead to less good adhesion. Examples of evolution of adhesion properties, depending on of viscoelastic properties, in the sector of photoreticulable coatings, are provided in the publication from Proceedings of 3 ^ Nurnberg Congress, European Coating Show, paper nº 3, March 1995, - Procedures of the 3rd Congress of Nurenberg, European coating sample, paper No. 3, March nineteen ninety five.

The main drawback of the systems described in the literature, it is not possible to increase, by same time, two properties such as flexibility and hardness. On the other hand, the adherence of the system decreases generally when the hardness of the material increases.

The present invention remedies the limitations and disadvantages of the prior art of the technique, and allows to increase the hardness of materials, such as the coating or molding products or composite materials, by the addition of specific crosslinked microparticles, preserving, at the same time, or eventually, improving, the level of flexibility of the material, improving at the same time the adhesion of the material on the substrate and, in a more in particular, on difficult substrates, such as polyolefins and, more particularly, polyethylene or polypropylene, and ethylene-propylene copolymers. Another advantage of microparticles of the invention, is its excellent compatibility, which allows, in this way, an incorporation, at high rates, without compatibility problem and no negative effect on the rheology of the compositions concerned, and the conditions of application, either of the coating compositions, or of the molding compositions.

In a more particular way, the present invention, allows the obtaining of coatings having a enhanced hardness and flexibility, with very good adhesion on polar or non-polar substrates and, in a more in particular, of thin bale coatings, less than 100 µm and, preferably, less than 50 µm, on substrates of difficult adhesion, such as polyolefins in general and, of a more particular form, polyethylene and polypropylene, without surface treatment. In effect, this is allowed thanks to the presence, in the compositions, of acrylic microparticles reticulated, new, of an essential composition and structure specific, of a size between 10 and 300 nm, adaptable to each application.

A first object of the invention refers to crosslinked microparticles of a size between 10 and 300 nm, obtained by polymerization of a composition of polymerizable, ethylenically unsaturated compounds, characterized by the fact that the composition of compolymerizable, includes:

- a first component A, which represents a molar percentage of 50 to 99% of the said composition, and that it is constituted by (meth) isobornyl acrylate and / or (meth) norbornyl acrylate and / or (meth) acrylate cyclohexyl and, optionally, in combination with a (meth) C 2 -C 8 alkyl acrylate and / or Cardura E10 methacrylate.

- a second component B, consisting of less for a monomer or oligomer, which involves at least two polymerizable ethylenic unsaturations, via radicals

- a third component C, consisting of less for a monomer or oligomer, which involves, in addition to a polymerizable ethylenic unsaturation via radicals, so minus a second reactive function, f1, different from unsaturation ethylenic,

with the possibility of chemical modification, by at least partial, of the initial functions f1, in functions f2, under the condition that, the functions f1, selected, do not react with each other, at the time of polymerization and that, the sum of components A, B and C, equal 100%. The term "(meth) acrylate", must be interpreted, at all times, as acrylate and / or methacrylate.

The preferred size of these microparticles is corresponding to a value ranging from 10 to 200 nm and, in a way more particular, from 20 to 100 nm. These can be obtained, in a way general, by radical polymerization, in emulsion in medium aqueous, or by dispersion polymerization, in non-aqueous medium, of said composition of polymerizable compounds. In the middle aqueous, there is a presence of an emulsifier and, in medium not aqueous, there is the presence of a stabilizing polymer, according to the common techniques known to the person skilled in the art of specialized technique, and described in the literature, as in Advances in Polymer Science, - Advances in polymer science -, (1988), volume 136, pages 139-234. The specificity of these particles is linked to its composition.

Component A may be constituted by a monomer or by a mixture of monomers, chosen from among (meth) acrylates of: isobornyl, norbornyl, cyclohexyl, in possible combination with an alkyl (meth) acrylate in C 2 -C 8 and / or (meth) Cardura acrylate E10 The alkyl (meth) acrylate in C_ {2} -C_ {8}, can represent a percentage molar component A, from 0 to 30%. In the case of the mixture (meth) isobornyl, norbornyl, cyclohexyl acrylates, Isobornyl (meth) acrylate represents, in a way preferable, a molar percentage of component A, of at least one fifty%.

The preferred component A is the (meth) isobornyl acrylate, with a preferred proportion of the polymerizable, in the composition, corresponding to a Molar percentage located between 60% and 90%. The (meth) C 2 -C 8 alkyl acrylates, they are chosen, preferably, from the (meth) acrylates of: ethyl, propyl, n-butyl, tert.-butyl, ethyl-2-hexyl and (meth) acrylate of Cardura E10. Compound B is constituted by a monomer or by an oligomer or by a mixture of monomers or of oligomers, or by a mixture of monomers and oligomers, chosen between:

- the di (meth) acrylates of ethylene glycol, propylene glycol, butanediol, methyl-2-propanediol, from Neopentyl glycol, hexanediol, zinc and / or calcium, tri (meth) glycerol acrylates, trimethylolpropane and / or alkoxylated derivatives, tri- or tetra- (meth) pentaerythritol acrylates and penta o hexa (meth) dipentaerythritol acrylates, oligomers of diols of polyethers, polyesters, polyurethanes of Mn less than 2500

- substituted or not substituted divinylbenzenes replaced

- oligomers of unsaturated polyesters or Acrylic acrylics of less than 2500 Mn, having a number of ethylenic unsaturations per mole, from 2 to 50, in one way preferred, from 2 to 20

with the proportions of component B in the composition of the polymerizable compounds, varying, in a way preferably, in a percentage ranging from 0.5% to 10% molar.

Component C is a functionalization agent of the microparticles of the invention. The F1 functions provided by component C, they may be identical or different, depending on whether the component C comprises one or more monomers and / or oligomers of f1 functions, identical or different, with the proviso that, in the case where functions f1 are different, they do not react between them, at the time of polymerization. The functions f1, are selected, in a preferred way, among the functions: epoxy, hydroxy, carboxy, carboxylic anhydride, isocyanate, silane, amine or oxazoline

Component C, is present, of a preferably, at a molar rate of at least 49.5%, with relation to the composition of tradable compounds A, B and C, and it is constituted, at least, by a monomer and / or oligomer selected from:

- (meth) acrylic acid, acid maleic, fumaric or itaconic, for f1 being a function carboxy

- maleic anhydride, itaconic anhydride, for f1 being a carboxylic anhydride function

- hydroxyalkyl (meth) acrylates, with a C2-C6 alkyl or mono (meth) acrylates of polyether oligomers of polyester- or polyurethane diols, or polycaprolactone of Mn less than 1500, for f1 being a function hydroxy

- glycidyl (meth) acrylate, (meth) acrylates of epoxidized derivatives of dichlopentadiene or epoxidized vinyl norbornene (meth) acrylates or (meth) alkoxylated glycidyl ether acrylates, or the (meth) acrylates of epoxidized cyclohexene derivatives, for f1 being an epoxy function

- the (meth) acrylate of isocyanate-ethyl and mono (meth) acrylates urethanes derived from diisocyanates, for f1 being an isocyanate function.

- the (meth) acrylates that carry a group trialkyl or trialkoxysilane, for f1 being a silane function

- dimethylaminoethyl (meth) acrylate, or (meth) tert.-butylaminoethyl acrylate, for f1 being a amine function

- he 2- (5-met) acryloyl-pentyl-1,3-oxazoline, for f1 being an oxazoline function.

In a more particular way, component C, is is present at a molar rate corresponding to a percentage It ranges from 5 to 30%, by weight, in relation to the sum of polymerizable components A, B, C and, this one, is selected from: the (meth) glycidyl acrylate, hydroxyalkyl (meth) acrylates in C 2 -C 6, (meth) acrylic acid, the anhydride or maleic acid, the anhydride or itaconic acid, the (meth) ethyl isocyanate acrylate, the (methyl) dimethyl aminoethyl acrylate.

The functions f1 provided by component C, they can be chemically modified, at least partially, to lead to the presence of modified f2 functions, born of functions f1, choosing functions f2, in a way preferred, among (meth) acrylates, vinyls, maleates, smokers, itaconates, alcohol esters allyl, unsaturations based on dicyclopentadiene, esters or unsaturated fatty amides in C 12 -C 22, the carboxylic acid salts or the quaternary ammonium seles.

The chemical modifications of the functions f1 in functions f1, can be performed according to the procedures already known in the literature. For example, the f2 functions:

- (meth) acrylates from the functions f1:

-

epoxy, by reaction with the acid (met) -acrylic

-

carboxy or anhydride, by reaction with glycidyl (meth) acrylate or (meth) acrylate hydroxyalkyl, with a hydroxyalkyl in C_ {2} -C_ {6}

- maleates or itaconatos, from f1 epoxy or hydroxy functions, by reaction with the anhydride maleic or itaconic

- salts of carboxylic acid, from F1 carboxy functions, by neutralization with a base such as soda, potash or ammonia or an amine

- quaternary ammonium salts, from the f1 tertiary amine functions, by reaction with a mineral acid or organic

- esters of allylic alcohols, from the f1 anhydride functions, by reaction of an allyl alcohol

- dichlopentadiene unsaturation (DCPD) from of the f1 carboxy functions, by reaction of adding the DCPD

- vinyl, from the functions f1 hydroxy, by reaction with a vinyl-azolactone, such as the 2-vinyl-4,4-dimethyl-azolatone, or vinyl isocyanate, such as the isocyanate of isopropenyldimethylbenzyl

- esters or unsaturated amides, in C_ {12} -C_ {22}, from the functions f1 anhydrous or carboxy, by reaction of an alcohol or an amine unsaturated fat in C 12 -C 22

A particularly preferred composition of the microparticles of the invention, comprise:

- a 50 to 95% molar percentage of a component A, consisting of isobornyl (meth) acrylate and / or norbornyl

- a 0.5 to 10% molar percentage of a component B, as defined above, above

- a molar percentage of a maximum of 49.5%, of a component C, as defined above, above, with the additional condition that, the sum of A + B + C = 100% cool

Among the preferred microparticles they carry, At first, functions f1, can be cited:

- microparticles that carry functions f1 carboxy, or f1 carboxy functions, partially or completely modified in functions f2 (meth) acrylates and / or maleates and / or fumarates and / or maleimides and / or carboxylic acid salts

- microparticles that carry functions f1 epoxy and / or hydroxy, or epoxy functions and / or hydroxy functions, partially modified in functions f2 (meth) acrylates and / or maleates and / or smokers and / or maleimides.

The (meth) acrylic and / or maleate functions and / or smokers, have an interest in crosslinkable compositions by radical means: either by means of UV rays, or electron beam, either through a thermal system radical initiation, such that they include a derivative peroxide, eventually, in the presence of an accelerator of decomposition.

The epoxy and / or hydroxy functions can participate in the photochemical crosslinkable compositions, in presence of a cationic photoinitiator, or via condensation. The carboxy functions have, above all, an interest in condensation reactions

The salts of carboxylic acids or ammonium Quaternary, have an interest in aqueous compositions, because to its water-dispersible or water-soluble functions, which convert the microparticles concerned in hydrodispersible or water soluble, in an aqueous-based application composition.

The double functionality f1 / f2, as carboxy (meth) acrylate or epoxy (meth) acrylate and / or maleate and / or fumarate, converts possibly the use of the microparticles concerned, in dual reactive systems, with a double cross-linking mechanism, by function f1 or f2. Therefore, the f1 / f2 functions of These crosslinked acrylic microparticles are adaptable, in function of application and host composition.

A second object of the present invention is a specific procedure for preparing the microparticles of the invention, which has the advantage of being simpler and more practical, in relation to those who are known in the state previous art of this specialized technique.

This procedure of preparation of microparticles of the invention, comprises a step of radical polymerization, by dispersion, in medium non-aqueous, non-solvent, polymer formed by a composition of polymerizable compounds A, B and C, as defined for the microparticles of the invention, without the need to add stabilizing polymer, for formed microparticles, or before, neither during, nor after polymerization, possibly being able comprise, said procedure, a supplementary stage of chemical modification, at least partial, of functions f1 contributed by component C, as defined in the invention.

This preparation procedure avoids, therefore therefore, the inconveniences linked to the presence of a polymer stabilizer:

- polymer availability problem stabilizer and solubility in the polymerization medium

- negative effect on technical performance of the microparticles, in terms of compatibility or reactivity of reactive functions.

The particularity of this procedure is is linked to the specific composition of the composition of the polymerizable compounds and, in a more particular way, to the nature of component A of the invention, as it has been defined above.

Among the particular advantages of microparticles obtained by this specific procedure, we can cite a compatibility and, as the case may be, a reactivity clearly improved, without limitation of availability or characteristics of the stabilizing polymer.

Moreover, its particular structure, obtained by means of the specific procedure used, confers, to the microparticles obtained, a character of self-availability and self-stabilization, in a solvent medium, identical or comparable to polymerization. At the same time, this procedure, it allows to obtain very crosslinked microparticles monodispersed, in terms of size, which is important to perform rheological technical performance and specific viscoelastic, in certain applications, in the sector of the coating compositions, of the molding compositions or of composite materials (composites).

The solvent used for this procedure, it is an organic solvent, or a mixture of organic solvents selected from among the alkanes in C 6 -C 10 such as hexanes, heptanes and, more particularly, the n-heptane, cyclohexane, octanes, nonanes and / or C 3 -C 5 alkanols, such as the isopropanol, butanol, pentanol. Mixtures of non-polar solvents, such as heptane, with solvents polar, such as ispropanol, to adjust the solvent power of the medium, in relation to the polymerizable compounds, by a part and, on the other, part, the non-solvent power of the medium that is becomes a means of precipitation, relative to the polymer formed. The weight ratio between alkane in C 6 -C 10 and alkanol in C_ {3} -C_ {5}, may vary from 0/100 to 75/25 and, in a more particular way, from 35/75 to 50/50. This one remains of a particular form, as preferred, in the case where, this mixture, it is based on n-heptane or cyclohexane, for one part, or isopropanol or butanol, on the other hand.

The weight ratio between the sum of the components A, B and C, on the one hand, and the solvent or mixture of Solvents, on the other hand, can vary from 10/90 to 75/25 and, from one preferred form, from 15/85 to 30/70. This relationship is one of the procedure parameters that allow adjusting the size of the microparticles The more the dilution increases, the more tendency to decrease has the size of the microparticles.

The dispersion polymerization of the compounds ethylenically unsaturated, it is done via radicals, by adding a radical initiator, current, to This type of polymerization, more adapted to the environment. Temperature polymerization, adapts to the decomposition temperature of the radical initiator chosen and, the boiling temperature of the solvent medium used may vary, in a general way, in function of the initiator and solvent medium used, within margins ranging from 20ºC to 150ºC. As an example of initiator, we can cite: the azic derivatives, such as the azobisisobutyronitrile (AIBN) and derivatives, peroxides and hydroperoxides, or any other initiation system, soluble in the polymerization medium and known by the person expert in the art of specialized technique. One more way In particular, these primers may be functionalized with a reactive function f3, such as hydroxy or carboxy, for example, hydroxylated or carboxylated sugar derivatives. In this case, the microparticles obtained, will be at least partially functionalized by f3 functions. Moreover, they can be used other radical initiators, which allow a radical polymerization called "controlled" or "alive", such as those described in Comprehensive Polymer Science, volume 3, pages 141-146, Pergamon, London, 1989. Similarly, transfer agents chain, such as mercaptans, may be associated to the initiator, to better control the masses molecular. The hardness of the polymerization will depend on the nature and of the initiator rate and the temperature of polymerization. The usual initiator rate may vary, within margins ranging from 0.05 to 5%, by weight, relative to the sum of the polymerizable components A, B and C.

According to a first embodiment of this procedure, in batches or "batch", all of the polymerizable components A, B and C are added, under the regime of stirring, from the beginning, in the reactor containing the entire of the solvent, and maintained at the polymerization temperature. The monomers, can also be added as a solution, in a part of the polymerization solvent. The initiation of the polymerization, is carried out under agitation, by means of progressive addition of the chosen radical initiator, soluble in The polymerization medium. After finishing adding the initiator, the polymerization, continues during a course of time that can vary from 1 hour to 8 hours, depending on the temperature, nature and the initiator's fee, nature and global concentration in polymerizable compounds. The self-stabilized formed microparticles in the polymerization medium, can be recovered, either by precipitation, by the addition of a non-solvent, such as an alcohol, in a proportion ranging from 2/1 to 5/1, by weight, in relation to the dispersion, precipitation, followed by filtration and drying, is that is, by a single stage and evaporation of the solvent medium dispersion, preferably, under reduced pressure which goes from 10 to 30 mbar.

The final particle size of the microparticles obtained, varies within a range of 10 to 300 nm and, preferably, within ranges that they range from 10 to 200 nm and, in a particular way, within about margins ranging from 20 to 100 nm, depending on the dilution of the polymerizable compounds, and the molar ratio of component A. To decrease the size of the microparticles, you can increase the rate of component A, or increase the dilution rate of polymerizable compounds, and / or increase the precipitating power of polymerization medium, and adjusting the nature and / or the polymerization solvent medium composition. The advantage essential to this procedure and its different ways of realization, is its simplicity and flexibility, in preparation of an important variety of microparticle structures, proceeding simply to vary the nature and proportions of components A, B and C, within the limits above defined of the invention.

According to a second embodiment of this procedure, this comprises one or several successive stages of polymerization, continuous and / or discontinuous, characterized respectively by an addition of polymerizable compounds, respectively, in continuous, or only once, per stage concerned. In the case where the procedure involves more than a step of discontinuous and / or continuous polymerization, the composition of the polymerizable, it can be identical or different from one stage to the other. Thus, in this way, it is possible to make structures of microparticles, very particular, multilayer type, depending on the composition of the polymerizable of each stage, and the order chronological of each continuous or discontinuous stage.

In the case where, the composition of the polymerizable behaves a compound C that functions functions f1, the procedure, as described above, may comprise, after the polymerization stage, a stage Supplementary chemical modification of function f1 and / or the function f2, born of f1. This chemical modification stage can take place, as appropriate, either before the recovery of the microparticles, by evaporation of the solvent from polymerization, either after the recovery of these microparticles, in which case, modification may take place chemical as the case may be, or in bulk, if the viscosity allows, at the temperature of the modification, or in solution, in a solvent different from that of the polymerization, if the latter does not suit, as regards its boiling temperature or its chemical inertia. As an example Preferred chemical modification, you can cite the (met) acrylation of reactive functions, such as: epoxy and hydroxy, by (meth) acrylic acid or anhydride or maleic acid or fumaric or itaconic acid or acid or anhydride carboxylic acid by glycidyl (meth) acrylate or hydroxyethyl- (meth) acrylate. So for example, the (met) acrylation, can take place in solution, containing, approximately 30-60% microparticles dispersed, in the presence of esterification catalysts such such as Cr (III) diisopropyl salicylate, the Cr (III) ethyl hexanoate bromide ethyltriphenyl phosphonium, tertiary amines.

A variant of this procedure can comprise, before the polymerization stage, a stage of dispersion, in the non-aqueous medium, of organic microparticles or minerals, insoluble in this medium, followed by a stage of polymerization, as described above. In this case, dispersed organic or mineral microparticles, they have sizes adapted to that of the final microparticles to obtain. The predispersed microparticles can be chosen from organic or mineral pigments, or organic fillers or additives or minerals, or the microparticles of the invention, previously prepared and insoluble in the dispersion medium. This variant of procedure, allows a batter or encapsulation, at least partial, simpler and more practical, of the microparticles polidispesadas, in order, for example, to improve their dispersibility in other dispersion media (aqueous or organic), or to improve its compatibility in host matrices for coating, molding or material compositions compounds.

A third objective of the invention relates to coating or molding compositions or materials "composite" type compounds, which comprise the microparticles of the invention, as defined previously.

These compositions, are crosslinkable or not crosslinkable, but, preferably, these are crosslinkable:

- either due to the presence of the microparticles of the invention, as defined previously

- either independently of the presence of the functions f1 and / or f2, that is, through the reactive functions of the initial composition, without the microparticles

- or by reactive functions typical of the initial composition, and through those of the microparticles

You can still distinguish between crosslinkable compositions, the compositions containing only, that is to say at a rate or percentage of 100%, or essentially, that is, at a percentage between 60 and 90% of the crosslinked acrylic microparticles that carry functions f1 and / or f2, identical or different, but that react between them to form, at least, a network of crosslinking that constitutes the matrix, either of a coating, or of a molding product.

For example, these compositions can be constituted solely or essentially by crosslinked acrylic microparticles, carrying f2 functions (met) radical crosslinkable acrylates, either by mediation of a radical, thermal initiation system, current, containing a peroxy compound and, eventually, a acceleration of decomposition, or by mediation of irradiation, by radiation such as UV, in the presence of a photoinitiator or electron beam, in the absence of a photoinitiator. Other examples illustrating these compositions can be cited, such as constituted coating or molding compositions solely or essentially by acrylic microparticles reticulated, which respectively carry functions co-reactive f1 epoxy and anhydride.

Another example of such types of compositions, in particular for coatings, is an aqueous coating composition, consisting solely or essentially of crosslinked acrylic microparticles, of the invention, bearing functions f1 and / or f2 or having a specific structure that convert them into water-soluble or water-dispersible, and that have characteristics of Tg and minimum temperature of film that allows their coalescence, at a temperature within a range between 0 and 40 ° C. Such types of functions f1 and / or f2 may be, for example, salts of carboxylic acids or ammonium salts and, more particularly, quaternary ammonium salts. As the specific structure of microparticles having this water-soluble or water-dispersible character, there may be mentioned the presence of acrylated oligomers based on polyethers, such as polyethylene glycol, in a preferred manner, of average molecular mass in number Mn, less than 2500, in a way preferred, less than
1500

In the case of coating compositions or molding or composites of the "composites" type, wherein, the crosslinked acrylic microparticles of the invention, they are reactive or non-reactive partial components, in the presence of other reactive or non-reactive components of the composition, the rate of these particles, may vary within ranges that range from 0.5 to 50%, by weight, in relation to the sum of Organic components of this composition. Out of microparticles of the invention, these compositions, comprise a base component, which is the basic organic matrix of the coating or molding product and additives or usual fillers adapted or adjusted, depending on the intended application and the predisposition of the person skilled in the art of this technique specialized.

As reactive or non-reactive additives, The microparticles of the invention can be used in the crosslinkable or non-crosslinkable coating or molding compositions crosslinkable, in a way to generate, to:

- reduce the viscosity of these compositions, allowing a better molding and a better application on substrates to be coated and, on the other hand, compositions of a greater dry extract and, consequently, of a lower compound rate volatile organic

- control better, by application specific, the rheology of these compositions, by adjustment of the structure of the microparticles

- reinforce or plasticize the matrix, depending on the compatibility, functionality and Tg of the microparticle, in relation to the host matrix.

The microparticles, as additives, do not reagents, can have functions selected from f1, f2, such as defined in the preceding invention, which, all and being chemically inert, with respect to the composition host, can significantly improve the compatibility of the microparticle, with respect to the host matrix, by favorable physicochemical interactions.

In the case of the microparticles used as reactive additives, their reactive functions, are selected and adapt or modify to react with reactive functions of the crosslinkable host composition, or between them. So by example, in the case of a crosslinkable composition via radicals, thermal or photochemical, containing monomers and / or ethylenically unsaturated mono- or multifunctional oligomers, the microparticles, after chemical modification, according to the stage of polymerization will preferably be polyunsaturated. The multi-epoxy or multi-hydroxy reactive microparticles, are will be adapted for coatings, epoxy compositions photoreticulable, cationically, in the presence of cationic photoinitiators, such as triarylsulfonium salts or of diarylsulfonium. The multi-epoxy reactive microparticles or multi-carboxylated, will be adapted for the cross-linking of coating or molding compositions based on epoxides and polyamines or carboxylated acrylic or anhydride copolymers of carbonic diacid.

Similarly, the microparticles partially neutralized multicarboxylates can serve as hydrodispersible microparticles or, depending on the degree of neutralization, water soluble, and can be used in compositions of coatings based on aqueous polymer dispersions reactive or non reactive. This character of hydrodispersibility or of water solubility, can also be conferred by a component C and / or B, which has constituents selected from, respectively, the mono- and di- (meth) polyether acrylates diols, such as polyethylene glycol of Mn less than 1500. Of a particular form, hydrodispersible microparticles or water-soluble bearing (meth) acrylic functions, after partial modification of its functions f1, can be used in photoreticulable coatings based on aqueous dispersions of polymers, preferably, acrylics. Microparticles Used as reactive additives, they have a true function crosslinking agent and system reactivity activator concerned, due to the fact of its high functionality.

The effect on technical performance, Mechanical, coating, or molded product, translates for enhanced reinforcement and flexibility, depending on the functionality, compatibility and Tg of the grafted microparticle chemically to the host matrix, behaving, the microparticle, as a grafted or not grafted microload and / or a hard or flexible. The cohesion energy of the final material, coating or molding product, is thus augmented, with a positive effect, possible, at the same time, on hardness and flexibility.

In addition to the hardness / flexibility commitment, the presence of the microparticles of the invention, makes possible a better adhesion of the compositions concerned, on various substrates, polar or non-polar. These substrates can be coated substrates by coating compositions, or impregnable, as loads or reinforcements, in the molding or composite compositions of the type "composites."

As examples of polar substrates on which, the compositions containing the microparticles of the invention, provide good adhesion, it is preferred to cite: glass, steel, aluminum, silicon, polycarbonate, wood, glass fibers, carbon fibers, fibers Polyamide polyester, cellulase fibers.

As examples of reputed non-polar substrates, difficult in terms of adhesion, which provide good technical adhesion performance with the compositions of coating and, preferably, with the compositions of Radical crosslinkable coating can be cited: polyolefins and, more particularly, polyolefin and polypropylene, with or without special surface treatment, and of low surface tension coatings, such as photoreticulated varnishes.

Among the preferred coating compositions that have a good hardness / flexibility / adhesion commitment
cia, on polar or non-polar substrates, a radical crosslinkable composition may be cited, containing a percentage comprised within ranges ranging from 0.5 to 50%, by weight, preferably, from 5 to 30 %, by weight, of crosslinkable acrylic microparticles of the invention, such as those previously defined, which preferably carry the reactive functions f2 (meth) acrylates and / or maleates and / or malimimides and, comprising, said coating composition, in addition, acrylic or vinyl mono- or polyfunctional monomers and / or mono- or pulifunctional acrylic oligomers or unsaturated polyester oligomers.

As mono- or multifunctional monomers acrylics, the acrylic monomers of a functionality in (meth) acrylic unsaturation per molecule, which range from 1 to 6. In a more particular way, these can select the following monomers and mixtures thereof: (meth) isorbonyl acrylate, (meth) acrylate isodecyl, (meth) lauryl acrylate, (meth) acrylate 2-2-ethoxy-ethoxy-ethyl, (meth) tetrahydrofuryl acrylate, (meth) acrylate 2-phenoxy-ethyl, (meth) acrylate of tridecyl, ethoxylated nonylphenol (meth) acrylate, di (meth) ethoxylated neopentyl glycol acrylate or propoxylated, polyethylene glycol di (meth) acrylate or polypropylene glycol, hexanediol di (meth) acrylate, tri (meth) ethoxylated trimethylolpropane acrylate and / or propoxylated

In the case in which, oligomers such as unsaturated polyesters are present in the composition, vinyl aromatic monomers, such as styrene or vinyltoluene or allyl phthalate.

Among the mono- or multifunctional oligomers that can be present in these compositions and, in a way Preferred, with acrylic monomers, may be mentioned: oligomers (met) acrylates of a functionality ranging from 1 to 50, chosen from: (meth) polyether acrylates (meth) polyepoxy acrylates, (meth) acrylates of polyesters, (meth) polyurethane acrylates, (meth) polycaprolactone acrylates or copolymers acrylics of at least one (meth) acrylic ester with the (meth) glycidyl acrylate, these copolymers, which are (met) acrilizan, then, at least partially, in A separate stage. The average molecular mass, in number, of these oligomers or copolymers, remains less than 20,000. In a case most particular of the composition, acrylic microparticles cross-linked bearing f2 (meth) acrylate functions, can completely replace the multifunctional monomer or oligomer of functionality ≥ 2, as a crosslinking agent with performance hardness / flexibility and adhesion techniques on the substrate, clearly improved.

These compositions can be crosslinked via of radicals:

- either by radical, thermal, in presence of a radical initiation system, thermal, which comprises a peroxide derivative, such as a peroxide or a ordinary organic hydroperoxide, if any, in the presence of a decomposition accelerator, such as a tertiary amine, or salts of cobalt, such as Co octoate, in proportions corresponding to those currently used by the person skilled in the art of this specialized technique and, of a general form, with a peroxide derivative rate, comprised within of margins between 0.5 and 6% and a rate of decomposition accelerator within a range located between 0.01 and 2%, in relation to the sum of monomeric components and / or oligomers, also being able to perform, cross-linking, based on temperature, based on presence, or not, of a decomposition accelerator of the peroxide derivative.

- either by irradiation, that is, UV radiation, in the presence of a photoinitiator system, commonly used in photoreticulable systems acrylics, such as aromatic ketones of the benzophenone type, α-hydroxyketones, derivatives α-dicarbonyls, acylphosphine oxides, in the presence or not of tertiary amines, in proportions ranging from 0.5 to 10%, relative to the sum of the monomers and / or oligomers of the composition, or by electron beam, in absence of photoinitiator

In a more particular way, a radical crosslinkable composition, intended to be applied, or that is applied, in the form of a coating, on polar substrates or non-polar, such as those defined above, above, and comprising:

- from 0.5 to 50%, by weight, and in a way preferably, from 5 to 30%, by weight, of microparticles such as those defined in any one of claims 1 to 7, that carry functions f2 (met) acrylates and / or maleates and / or smokers and / or meleimides and / or vinyls

- from 50 to 95%, of at least one monomer chosen from isobornyl (meth) acrylate and / or the (meth) isodecyl acrylate, (meth) acrylate 2-2-ethylethoxy ethyl, (meth) tridecyl acrylate, (meth) lauryl acrylate, (meth) tetrahydrofuryl acrylate, (meth) acrylate 2-phenoxy ethyl

- from 0 to 5%, by weight, of (meth) alkylene diol acrylate in C_ {2} -C_ {6}, choosing the percentages of such a way that, the total sum of the microparticles and monomers, equal 100%.

In an even more preferred way, this composition, is crosslinkable by irradiation, either by UV radiation, or already by electron beam. He preferred thickness of crosslinkable coatings via radicals, it is less than 100 micrometers and, in a more particular, less than 50 micrometers.

A particular case of the composition of radical crosslinkable coating, is a composition of aqueous dispersion of crosslinkable polymer, comprising hydrodispersible or reactive water-soluble microparticles, which They participate in crosslinking. The aqueous polymer dispersion crosslinkable, it can be an acrylic emulsion that can already contain a water soluble or hydrodispersible crosslinking agent, based on acrylic multifunctional monomers and / or oligomers of functionality ≥ 2, water dispersible or water soluble. The microparticles of the invention carry, for example, f2 functions (met) acrylates that can replace, in part, or completely, an acrylic cross-linking agent, multifunctional, water dispersible or water soluble, of this type. The hydrodispersability or water solubility of such types of microparticles, it is insured, in such a case, by f1 and / or f2 water soluble functions, such as the salts of carboxylic acid or quaternary ammonium salts, or by a specific, water-soluble structure of a constituent of component C of the microparticle, chosen, for example, among the (meth) polyethylene glycol acrylates or other diols polyethers, water soluble or water dispersible, a dispersion composition aqueous polymer, may also comprise polymers that involve own reactive functions of this polymer, which can participate in crosslinking. The crosslinking of these compositions of aqueous polymer dispersion containing the microparticles of the invention is realized, after the application of a film of film of this composition, on a substrate, either either by thermal radical route, or by UV radiation, or electron beam.

Another preferred coating composition of The invention is a crosslinkable composition comprising derivatives epoxides and the microparticles of the invention, and that is crosslinkable, either by UV radiation, in the presence of a cationic photoinitiator, or by condensation reaction with at least a second reactive component, selected from: polyamides and / or carboxy functionalized polymers or copolymers or carboxylic anhydride.

The epoxidized derivatives are selected from the monomers, oligomers or copolymers or epoxidized resins, of a functionality ranging from 1 to 50. In a more particular way, in the case of photochemical crosslinkable compositions, in presence of a cationic photoinitiator, monomers or oligomers epoxidized, they are, preferably, of a structure cycloaliphatic Among the cycloaliphatic epoxidized derivatives, we can mention: the epoxidized cyclohexene, the carboxylate of 3,4-epoxycyclohexylmethyl-3 ', 4'epoxycyclohexane, the cycloaliphatic epoxides described in the patent documents International WO 98/28286 or WO 98/45349.

In the case in which the compositions are Photochemical cationic crosslinkable, the microparticles of the invention, in a preferred way, are chosen from among microparticles that carry functions f1 epoxy and / or hydroxy. The condensation crosslinkable composition, comprises, in a way preferably, microparticles that carry functions f1 epoxy and / or hydroxy and / or carboxy and / or anhydride and / or isocyanate and / or amine.

The coating compositions of the invention, also apply to compositions comprising at least one reactive resin selected from: the alkyds or unsaturated polyesters, or saturated polyesters or polyamides or polyurethanes or polyureas, with microparticles of the invention, which preferably, the functions f1 and / or f2 reactive, with at least one function carried by this resin or reactive resins (s).

The functions f1 and / or f2, thus allow better anchoring of the microparticles, in the organic matrix, with a better reinforcement and / or flexibilization effect of the matrix organic For example, in the case of alkyd resins, the functions f1 and / or f2, can be secant functions such as unsaturations based on dicyclopentadiene or allyl esters or of esters of unsaturated fatty amides.

In the case of unsaturated polyesters, the f2 functions, can be (meth) acrylates and, in a way preferential, maleate or smoking. Functions f1 can be intended, such as anhydride or isocyanate, such that they are co-reactive with the terminal OH functions, carried by unsaturated polyester. They can for example The objective is to carry out F1 carboxy functions for maturation of unsaturated polyesters by magnesia, according to a maturation procedure by magnesia, which is fine known by the person skilled in the specialized art of The technique. F1 functions can be intended as an objective analogous, and adapt by the person skilled in the art specialized technique, in this case: saturated polyesters, polyamides or polyurethanes or polyureas. These compositions of coating, may comprise, in addition to the components reagents, other additives or usual fillers adapted to the specific need of each final application.

The invention also concerns compositions of molding or composites of the "composites" type, the which may be molding compositions comprising fillers and / or reinforcement. These molding or composite compositions, they can comprise at least one reactive resin, selected among unsaturated polyesters, dicyclopentadiene resins, vinyl esters, epoxides and polyamines or polyurethanes and polyureas or polyurethane-ureas or cyanates esters or bismaleimides, with microparticles of the invention, which preferably carry functions f1 and / or f2 reactive, with at least one function carried by this or these reactive resin (s).

The molding compositions containing the microparticles of the invention may comprise mineral fillers and / or organic and / or reinforcements chosen from: glass fibers, glass felts, carbon fibers, fibers cellulose, polyester or polyamide fibers.

A particular advantage of the microparticles of The invention resides in the fact that these allow a reduction of the viscosity of the coating compositions or of molding and, consequently, a significant reduction in reactive or non-reactive diluents, so that they are respected in a better way, the limitations of the environmental environment. So, In this way, these microparticles allow, through their presence, simultaneously: respect for a reduced rate of Volatile organic compounds (VOC), incorporating fees higher loads or additives, and improved properties mechanics of the materials concerned with coating or molding or of composite materials of the "composite" type. In a way more particular, the presence of these microparticles that have a functionality adapted to each application, allows a good compromise hardness / flexibility and adhesion on various substrates and more particularly difficult.

The sector of application of these compositions, It is broad, and includes: protective varnishes, paints, adhesives, inks, powdered materials, for coatings, powdered materials, for molding, molded parts, composite materials of the type "composite."

The examples given below, illustrate the objects of the invention.

Examples General Experimental Conditions Substrates

The photoreticulable formulations are deposited on the following substrates:

- Aluminum Q panel (dimensions panels: 0.6 x 76 x 152 mm 3, supplied by LABOMAT ESSOR), degreased with ethyl acetate

- Glass (cleaned with acetone)

- Polycarbonate (SCEX signature LEXAN plate PLASTIQUE, thickness 2 mm)

- Polypropylene (reference PP101460, supplied by GOODFELLOW, thickness 0.5 mm)

- Low density polyethylene (ET reference 11452, supplied by GOODFELLOW, thickness 0.5 mm).

Polycarbonate, polyethylene and polypropylene, se previously cleaned with ethanol, before applying coating.

By necessity of certain characterizations (by example, adhesion measurement), polyolefin substrates (polyethylene and polypropylene), are treated by the procedure of Corona, before the deposition of the formulation (according to conditions described in Int. Pol. Sci. Technol. No. 8, 1996, page 630).

Photoreticulable coating formulas

In the examples presented below, are obtained by radical polymerization of a photoreticulation formulation, under medium pressure UV lamp, of FUSION type (electrical power: 120 W / cm), after 6 passes to 4.6 m / minute These conditions ensure, in any case, a Maximum conversion of double acrylate bonds.

Characterization Measurement viscosity measurement

The viscosity of the formulations photoreticulable, it is a very important parameter for the application of light-cured films and obtaining coatings Of reduced thickness. In all of the following part, to then the viscosities of the formulations are measured with the help of a cone-flat, tension viscometer imposed, of the type CARRI-MED CSL 100 (CSL RHEOMETER) at a temperature of 20 ° C, during a gradient scan of shearing.

Hardness measurement of light-curing films

Hardness is measured by microidentification instruments (FISCHERSCOPE H100 device) at a temperature of 23ºC. The cutter is a Vickers pyramid of an angle, in the cusp of 136º. The hardness values presented in the part that continue, correspond to the "universal" hardness values, calculated according to the expression

H_ {u} = \ frac {P} {K \ delta 2

where, P, is the maximum load imposed, δ, is the notched depth, and k, is a constant dependent on the geometry of the cutter. The load P, is determine in this way that:

i) the notched depth, is less than 1/5 of the total thickness of the film

ii) the measured hardness is substantially constant With the low cut thickness.

The films are systematically analyzed, 24 hours after polymerization, and stored at a temperature of 23 ° C, and at 50% relative humidity.

Measurement of coating flexibility

The flexibility of substrate systems, It is estimated by the test test of "T-bend." The test test in question, it consists of winding the coated substrate on itself, and in determine the number of turns, from which, the coating located on folds or wrinkles, it is no longer damaged. Laps successive, are designated by 0 T, 0.5 T, 1 T, ... (see description of the test test in Lowe C., Rad. Cur., Volume 183, No. 4337, page 464). In all cases, the thickness of the films, is less than 50 µm and, more generally, of order of 20 µm.

The substrate used is an aluminum of the type panel Q, described above, above.

The test test of the T-bend, is performed with the help of a manual press. The observations to the Binocular magnifying glass (amplification x 12). Good flexibility, corresponds, in a general way, to a value less than or equal to 2 T.

The films are systematically analyzed 24 hours, after crosslinking, and stored at a temperature of 23 ° C, and at 50% relative humidity.

Measurement of the mechanical properties of the free film, a great deformations

The mechanical properties of the films free, at large deformations, are measured in uniaxial traction, at constant speed (1 mm / minute), and at room temperature. The specimens obtained in this way are marked with two tablets reflective, spaced 20 mm apart, so that they follow the elongation, during deformation, with the help of a external extensometer The effective dimensions of the sample are in a typical way, 20 x 4 x 0.1 mm 3.

Measurement of adhesion properties

The adherence of the systems is estimated by the grid test test (ISO 2409 Standard), on substrates specified above, above. A note that goes from 0 to 5, rate the resistance of the plotted film (divided into zones), when it is peeled, by means of an adhesive known force (the value "0" indicates that the film has remained completely on the substrate; "5" indicates that the film, it has been completely peeled). In our case, the strength of Peeling of the adhesive used (from TESA), For the grid test test, it is 240 ± 5 cN / cm (measured at 180º, on stainless steel plate). The thickness of the coatings, is of the order of 20 µm.

The films are systematically analyzed 24 hours after polymerization, and stored at a temperature of 23 ° C, and at 50% relative humidity.

Abrasion Resistance Measurement

Abrasion resistance is measured by TABER test test, according to NTF 30-015 (device 5150 ABRASER of TABER INDUSTRY). The test test, it consists of measuring the loss of mass, dragged by two wheels abrasive, after 100 hours.

The films are systematically analyzed over a period of 24 hours, after polymerization, and are stored at a temperature of 23 ° C, at 50% relative humidity

Chemical resistance measurement

The resistance of the coatings, to a chemical aggression, is endorsed by the test test called "rub-test" consisting of measuring time, before the total deterioration of the film, when proceeding to apply, to the surface of the latter, a circular motion and continuous, with the help of a solvent soaked cloth. In the cases that are subsequently treated, then the solvent, It is methyl ethyl ketone (MEK). The Films are made on glass plates.

The thickness of the coating is maintained constant, and is within a range located between 40 and 50 µm, in all cases.

Example 1 Synthesis of Crosslinked Polymeric Microparticles (MPR)

131.3 g of n-heptane and 131.5 g of propanol-2, in a 500 ml reactor, equipped with a refrigerator and with a mechanical agitation, and under a slight flow of nitrogen. The temperature, is brought to a level of 70 ° C. We proceed, to then, to load into the reactor, a mixture of monomers (meth) acrylics of the composition given below, to continuation:

- isobornyl acrylate: 69.80 g, that is, 76% molar (relative to monomers)

- hexanediol diacrylate: 5.02 g, that is, 5% molar (relative to monomers)

- glycidyl methacrylate: 11.96 g, that is, 19% molar (relative to monomers)

The temperature stabilizes at a temperature 70 ° C, and 0.78 g of azobisibutyronitrile (ie 10 mmol / l, relative to the monomers), in the reactor. Dispersion, remains transparent and homogeneous, of reduced viscosity, during The entire duration of the synthesis. At the end of 5 hours of reaction, the conversion of monomers, is greater than 95%, according to product tracking, by chromatography of steric exclusion, and by measuring the solids rate in the solution. The MRPs formed are isolated by distillation of the Synthetic solvents: the refrigerant is replaced by a distillation column, and 87.5 g of toluene are added and, the temperature, increases progressively, to a level of 105 ° C.

The MPR is then acrylated, by reaction with acrylic acid, at a temperature of 100 ° C, in the presence of a reaction catalyst, 0.8% by mass of the chromium III isopropyl salicylate, and 0.3%, by mass, of hydroquinone, to avoid any radical polymerization of acrylic functions. The chemical modification is developed at 50% of solids, in solution in toluene, in a 250 ml reactor of capacity, equipped with a refrigerator and a mechanical stirrer, under a slight flow of nitrogen. Acrylic acid is introduced in a slight excess, in relation to the epoxy groups, of such so that, the relation of the concentrations in function is: [acid] / [epoxide] = 1.05. At the end of the chemical modification, the MRP, are isolated by vacuum drying (20 mbar), at the temperature ambient. The final conversion of the epoxidized groups is 95%, which corresponds to a concentration in acrylic double bonds reagents of [C = C] = 9.1 10-4 mol / g. The dried MRPs are they are in the form of a solid, which can be milled in the form of A fine powder.

The size and mass of the MPRs are determined using a LASER light diffusion technique, multiple angles (reference: DAWN of WYATT TECHNOLOGY, operating at 632 nm), in the Chromatography column output, by exclusion steric The molar mass and the size of the MPRs are:

M_ {w} = 5.8 10 5 g / mol and R z = 3.1 nm

The temperature of the beginning of the zone of glass transition T_ {g} onset of these MPRs, measured by differential calorimetric analysis is 62 ° C.

Example 2

A composition was made photoreticulable reference (F1), consisting of 100 parts (in weight) of:

- 47.5 parts of isobornyl acrylate (SR 506, CRAY WALLEY)

- 47.5 parts of an acrylated oligomer referenced PRO 971 from SARTOMER

- 3 parts of Darocur 1173 (CIBA GEIGY)

- 2 parts of Irgacure 184 (CIBA GEIGY)

at room temperature Acrylated oligomer PRO 971, is a copolymer obtained via radicals, corresponding to the product sold in dilution referenced CN 818, by the firm SARTOMER and composed of:

- butyl acrylate

- methyl methacrylate

- glycidyl methacrylate

The glycidyl function of the oligomer was modified. in 2nd stage, by reaction with acrylic acid, to provide the acrylated oligomer.

In order to evaluate the contribution of MPR on the commitment plan hardness / flexibility / adhesion of the film final, the following photoreticulable formulation was made (F2):

over 100 parts:

-

47.5 isobornyl acrylate parts (SR 506, CRAY VALLEY)

-

19 acrylated MPR parts of example 1

-

28.5 parts of PRO 971 (SARTOMER)

-

3 parts of Darocur 1173 (CIBA GEIGY)

-

2 parts of Irgacure 184 (CIBA GEIGY)

The two formulations have a very high viscosity. next, at a temperature of 20 ° C. The results of Table I, show the fact that the formulation F2 has a character reofluidifying

The properties of the movies corresponding, are compiled in Table II. The coatings thicknesses, for hardness measurement, are of the order of 80 to 100 µm.

TABLE I

Viscosity values of formulations at 50 and 2150 s -1, measured at a temperature of 20 ° C Formulation Shear gradient (s -1) Viscosity (Pa.s) F1 fifty 2 250 2 F2 fifty 1.77 250 1.64

TABLE II

Summary of the physical properties of films obtained from F1 and F2 Hardness Flexibility Resistance to gridded Resistance (N / mm2) "T-Bend" on glass (adhesion) chemistry (s) F1 42 1.5 T 5 80 ± 10 F2 76 1.5 T one 80 ± 10

Example 3

The MPRs of Example 1 are introduced, in a mixture of acrylic monomers (mixture A) as follows:

-

Isobornyl Acrylate (SR 506): 60% in mass

-

isodecyl acrylate (SR 395, Provenance, CRAY WALLEY): 38% by mass

-

hexanediol diacrylate (SR 238): 2% in mass

Formulations are made photoreticulated based on the mixture A, and containing different Mass concentrations The compositions are found compiled in Table III

TABLE III

Compositions of different formulations used in example 3 (over 100 parts) Formulations Mix A MPR Darocur 1173 Irgacure 184 F3 (Ref) 95 0 3 2 F4 90.25 4.75 3 2 F5 87.9 7.1 3 2 F6 85.5 9.5 3 2

TABLE III (continued)

Formulations Mix A MPR Darocur 1173 Irgacure 184 F7 80.75 14.25 3 2 F8 76 19 3 2 F9 66.5 28.5 3 2 F10 57 38 3 2

TABLE IV

Formulations values at a temperature of 20ºC Formulations Gradient shear (s -1) Viscosity (Pa.s) F6 fifty 0.04 250 0.03 F8 fifty 0.18 250 0.14 F9 fifty 0.65 250 0.50 F10 fifty 2.78 250 2.16

The physicochemical properties (hardness, flexibility, chemical resistance) of the different coatings are presented in Table V in a compiled form. The thicknesses of the films, for the measurement of hardness, are from 20 to 25 µm.

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TABLE V

Properties physicochemical coatings Formulations Hardness (N / mm2) Flexibility "T-Bend" Chemical resistance (s) F3 (to) 0 T 20 ± 10 F8 = 5 1 T 55 ± 10 F9 52 one T 65 ± 10 F10 80 1.5 T 60 ± 10 (a): not measurable (value too weak)

Table VI presents the test results. Abrasion test, compared with the values obtained with a coating taken as an example of comparison, which presents a Good abrasion resistance. The abrasion properties are they measure on films of a thickness ranging from 60 to 100 µm.

TABLE VI

Abrasion properties of coatings Formulations Abrasion resistance (mg) Remember the values of hardness (N / mm2) F3 16.3 - ^ (a) F9 36 52 F10 40.8 80 Reference (b) 30 14 (a): not measurable (value too weak) (b): comparison for 100 p of the emulsion

- 20 p. CN976 (origin CRAY WALLEY)

- 52 p. CN550 (origin CRAY WALLEY)

- 23 p. CN501 (origin CRAY WALLEY)

- 3 p. Darocur 1173

- 2 P. Irgapure 184

Table VII presents the measurements of adhesion on different substrates.

TABLE VII

Properties coating adhesion Formulations Aluminum Glass Polycarbonate Polyethylene Polycarbonate PE trat. PP Trat (PC) (PE) (PP) Crown Crown F3 0 0 0 5 5 5 5 F4 0 0 0 5 5 5 5 F5 0 0 0 5 0 0 0 F6 0 0 0 0 0 0 0 F7 0 0 0 0 0 0 0 F8 0 0 0 5 0 0 0 F9 0 0 5 5 5 0 0 F10 0 0 5 5 5 5 5

These examples perfectly illustrate an increase simultaneous adhesion and hardness properties, in the case of the coatings containing the MPRs of the invention.

Example 4

The formulation made contains:

-

46.55 parts (weight) of isobornyl acrylate (SR 506)

-

19.95 p. from 2-2 (ethoxy-ethoxy) -ethyl (SR 256 of CRAY VALLEY)

-

28.5 p. MPR example 1

-

3 p. Darocur 1173

-

2 P. Irgapure 184

The mechanical properties measured at a temperature of 23 ° C, on the free film, are:

Young's module = 130 MPa

Elongation at break = 70%.

Breaking strength = 12.5 MPa

These results, illustrate, for this coating, a good commitment hardness / flexibility, with a good adhesion of the coating on glass and aluminum. The movie of reference, without MPR, is extremely fragile in terms of breakage, with a practically zero elongation at break, which does not allows to be characterized according to the procedures described before

Claims (25)

1. Crosslinked microparticles of a size between 10 and 300 nm, obtained by polymerization of a composition of polymerizable, ethylenically unsaturated compounds, characterized by the fact that the composition of the compolymerizable comprises: - a first component A, which represents a molar percentage of 50 to 99% of the said composition, and that it is constituted by (meth) isobornyl acrylate and / or (meth) norbornyl acrylate and / or (meth) acrylate Cardura E10 cyclohexyl and / or methacrylate and, optionally, in combination with an alkyl (meth) acrylate in C_ {2} -C_ {8}. - a second component B, consisting of least for a monomer or oligomer, which involves at least two polymerizable ethylenic unsaturations, via radicals, being constituted, component B, by a monomer or by a oligomer or by a mixture of monomers or oligomers, or by a mixture of monomers and oligomers, chosen from: - the di (meth) acrylates of ethylene glycol, propylene glycol, butanediol, methyl-2-propanediol, from Neopentyl glycol, hexanediol, zinc and / or calcium, tri (meth) glycerol acrylates, trimethylolpropane and / or alkoxylated derivatives, tri- or tetra- (meth) pentaerythritol acrylates and penta o hexa (meth) dipentaerythritol acrylates, oligomers of diols of polyethers, polyesters, polyurethanes of Mn less than 2500 - substituted or not substituted divinylbenzenes replaced - oligomers of unsaturated polyesters or Acrylic acrylics of less than 2500 Mn, having a number of ethylenic unsaturations per mole, from 2 to 50 - a third component C, consisting of less for a monomer or oligomer, which behaves, in addition to a polymerizable ethylenic unsaturation via radicals, so minus a second reactive function, f1, different from unsaturation ethylenic, with the possibility of chemical modification, by at least partial, of the initial functions f1, in functions f2, under the condition that, the functions f1, selected, do not react with each other at the time of polymerization, and being, the sum of the components A, B and C, of 100%. 2. Microparticles according to claim 1, characterized in that they carry functions f1 provided by component C, selected from: epoxy, hydroxy, carboxy, carboxylic anhydride, isocyanate, silane, amine, oxazoline and, eventually, functions f1, at least partially modified in functions f2, selected from: (meth) acrylates, vinyls, maleates, meleimides, itaconates, esters of allyl alcohols, unsaturations based on diglycpentadiene, esters or unsaturated fatty amides in C 12 -C_ {22}, carboxylic acid salts or quaternary ammonium salts. 3. Microparticles, according to any one of claims 1 or 2, characterized in that the component C is present in a molar percentage of at most 49.5%, in relation to the sum of the polymerizable, and is selected from: glycidyl (meth) acrylate, C2-C6 hydroxyalkyl (meth) acrylates, (meth) acrylate acid, maleic anhydride or acid or fumaric acid, the anhydride or itaconic acid, the isocyanotoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (5-methacryloyl-pentyl) 1,3-oxazoline. 4. Microparticles according to any one of claims 1 to 3, characterized in that the composition of the copolymerizable comprises: - from 50 to 95% of a component A, consisting of (meth) isobornyl acrylate and / or (meth) norbornyl acrylate and / or (meth) acrylate butyl - from 0.5 to 10% of a component B, consisting of at least one monomer and / or oligomers selected from: - the di (meth) acrylates of: ethylene glycol, propylene glycol, butanediol, methyl-2-propanediol, neopentyl glycol, hexanediol, diols oligomers of Mn less than 2500, polyethers, polyesters, polyurethanes - substituted or not substituted divinylbenzenes replaced - unsaturated polyester oligomers or acrylic oligomers of Mn less than 2500, having a number of ethylenic, molar unsaturations, from 2 to 50 - a molar percentage of a maximum of 49.5%, of a component C, consisting of at least one monomer and / or oligomer selected from: - (meth) acrylic acid, acid maleic, fumaric or itaconic, for f1 being a function carboxy - maleic anhydride, itaconic anhydride, for f1 being a carboxylic anhydride function - hydroxyalkyl (meth) acrylates, with a C2-C6 alkyl or mono (meth) acrylates of polyether oligomers of polyester- or polyurethane diols, or polycaprolactam, of Mn less than 1500, for f1 being a function hydroxy - glycidyl (meth) acrylate, (meth) acrylates of epoxidized derivatives of dichlopentadiene or epoxidized vinyl norbornene (meth) acrylates or (meth) alkoxylated glycidyl ether acrylates, or the (meth) acrylates of epoxidized cyclohexene derivatives, for f1 being an epoxy function - the (meth) acrylate of isocyanate-ethyl and mono (meth) acrylates urethanes derived from diisocyanates, for f1 being an isocyanate function. - the (meth) acrylates that carry a group trialkyl or trialkoxysilane, for f1 being a silane function - dimethylaminoethyl (meth) acrylate, or (meth) tert.-butylaminoethyl acrylate, for f1 being a amine function - he 2- (5-met) acryloyl-pentyl-1,3-oxazoline, for f1 being an oxazoline function being, the sum of A + B + C equal to 100% 5. Microparticles according to any one of claims 1 to 4, characterized in that they carry f1 carboxy functions, or f1 hydroxy functions partially or completely modified in f2 (meth) acrylates and / or vinyls and / or functions maleates and / or smokers and / or maleimides and / or salts of carboxylic acid. 6. Microparticles according to any one of claims 1 to 5, characterized in that they carry f1 epoxy and / or hydroxy functions, partially modified in f2 (meth) acrylate functions. 7. Method of preparing microparticles, as defined in any one of claims 1 to 6, characterized in that it comprises a stage of dispersion polymerization, via radicals, in a non-aqueous medium, not solvent, of the polymer formed, of a composition of polymerizable compounds, as defined in any one of claims 1 to 4, without any addition of stabilizing polymer for the microparticles formed, neither before, nor during, nor after polymerization, the aforesaid process may possibly comprise a supplementary stage of at least partial chemical modification of the functions f1 provided by component C, as defined in any one of claims 1 to 3 and 4. 8. Composition of coatings, or molding or composite materials of the "composites" type, characterized in that it comprises microparticles as defined in any one of claims 1 to 6. Composition according to claim 8, characterized in that it is crosslinkable, and is constituted solely or essentially by microparticles as defined in any one of claims 1 to 6, which carry functions f1 and / or f2, identical or different, crosslinkable between microparticles, and that form at least one crosslinking network. 10. Composition according to claim 8, characterized in that it comprises 0.5 to 50%, by weight, of microparticles as defined in any one of claims 1 to 6. 11. Composition according to any one of claims 8 to 10, characterized in that the said composition is a coating composition. 12. Composition according to claim 11, characterized in that the coating composition is a radical crosslinkable composition comprising acrylic or vinyl mono or multifunctional monomers and / or multifunctional acrylic oligomers and microparticles defined according to any of claims 1 to 6, which carry functions f2 (meth) acrylates and / or maleates and / or smokers and / or maleimides, born from the at least partial modification of the functions f1 starting. 13. Composition according to claim 11 or 12, characterized in that the coating composition is a crosslinkable composition by irradiation. 14. Composition according to claim 12 or 13, characterized in that the crosslinkable composition comprises, as acrylic monomers, (meth) isorbonyl acrylate and / or (meth) isodecyl acrylate, and / or (met ) lauryl acrylate and / or 2-2- (ethoxy-ethoxy) -ethyl and / or (meth) tricidyl acrylate, 2-phenoxy-ethyl (meth) acrylate and / or (meth) acrylate acrylate of tetrahydrofuryl, and / or, as acrylic oligomers, at least one acrylic oligomer chosen from: (meth) polyether acrylates, (meth) acrylates of polyesters, (meth) acrylates of polyurethanes, (meth) acrylates of polycaprolactone, (meth ) epoxy acrylates and (meth) acrylated acrylic copolymers. 15. Composition of coatings, as defined in any one of claims 11 to 13, characterized in that it is intended to be applied, or applied, as a coating, to polar and non-polar substrates , and includes: - from 0.5 to 50% and, preferably, 5 to 30%, by weight, of microparticles as defined in any one of claims 1 to 6, which carry functions f2 (met) acrylates and / or maleates and / or smokers and / or maleimides - from 50 to 99.5%, by weight, of at least a monomer chosen from isobornyl (meth) acrylate and / or the (meth) isodecyl acrylate or (meth) acrylate of lauryl, (meth) tridecyl acrylate - from 0 to 5%, by weight, of di (meth) alkylene diol acrylate in C_ {2} -C_ {6} choosing, the percentages, of such so that the total sum of microparticles and monomers is equal to 100% 16. Coating composition according to claim 15, characterized in that: - the polar substrates are: glass, steel, aluminum, silicon, polycarbonate, wood, glass fibers, carbon fibers, cellulose fibers, polyester or polyamide fibers - non-polar substrates, are: polyolefins and, more particularly, polyethylene, the polypropylene and ethylene-propylene copolymers with or without special surface treatment, and reduced coatings surface tension. 17. Composition according to claim 15 or 16, characterized in that it is applied to the substrate, in the form of a thin film, of a thickness of less than 100 micrometers, preferably of less than 50 micrometers. 18. Composition, according to claim 11, characterized in that said composition is coated, it is an aqueous dispersion composition, of crosslinkable polymer, comprising reactive, water-soluble or water-soluble microparticles that participate in the cross-linking. 19. The coating composition according to any one of claims 8 to 11, characterized in that said composition is a composition comprising epoxidized derivatives. 20. The coating composition according to claim 19, characterized in that it is crosslinkable by UV radiation, in the presence of a cationic photoinitiator, and comprises microparticles carrying f1 epoxy and / or hydroxy functions. 21. The coating composition according to claim 19, characterized in that it is crosslinkable by condensation reaction with at least one second reactive component selected from: polyamines and / or functionalized polymers or copolymers carboxy or carboxylic anhydride. 22. Composition of coatings according to claims 19 and 21, characterized in that, in the case where, the composition is crosslinkable by condensation reaction, this comprises microparticles carrying functions f1 and / or f2 epoxy and / or hydroxy and / or carboxy and / or anhydride. 23. Composition according to any one of claims 8 to 11, characterized in that this composition comprises at least one reactive resin selected from; unsaturated alkyl or polyester polyesters or polyester or polyamides or polyurethanes or polyureas, and microparticles as defined in any one of claims 1 to 6, behaving preferably reactive functions f1 and / or f2, with less a function carried by this or these reactive resin (s). 24. Molding composition according to claim 8 to 10, characterized in that it comprises at least one reactive resin selected from among: unsaturated polyesters, dicyclopentadiene resins, vinyl esters, epoxides and polyamines or the polyurethanes and polyureas or polyurethane-ureas and microparticles as defined in any one of claims 1 to 6, behaving, preferably, functions f1 and / or f2, reactive with at least one function carried by this or these reactive resin (s). 25. Molding composition according to claim 24, characterized in that it comprises mineral and / or organic fillers and / or reinforcements chosen from: glass fibers, glass felts, carbon fibers, Cellulose fibers, polyester or polyamide fibers.